Green Oxidation of Isochromans to Isochromanones with Molecular Oxygen Catalyzed by a Tetranuclear Vanadium Cluster

Comprehensive Summary Isochromanone is the core structure of many bioactive compounds.Direct oxidation of isochromans is one of leading methods for the construction of isochromanones,while most established processes remain suffering from the use of environmentally unfriendly metal oxidants,harsh reaction conditions,and the difficulty in catalyst recycling and product separation.Herein,we report a convenient,cost-effective,and green method for the synthesis of high-value added isochromanones via isochroman oxidations with O_(2) by a novel heterogeneous vanadium cluster catalyst(Cat.1)under mild conditions.This reaction protocol demonstrates high catalytic activity with good catalyst recyclability and reusability for a wide scope of substrates.

Ni_(4)-thiacalix[4]arene sandwiched Mo_8 polyoxometalate bimetallic nanoclusters for electrocatalytic glucose oxidation

Available online two new Ni_(8)Mo_(8) bimetallic coordination clusters,[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(PO_(4))](+Solvent)(Ni_(8)PMo_(8),H_(4)TC4A=p-tert-butylthiacalix[4]arene) and[Ni_(4)(TC4A)]_(2)[(Mo_5~VMo_(3)~ⅥO_(24))(OH)(CO_(3))](+Solvent)(Ni_(8)Mo_(8)),were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction,powder X-ray diffraction,FT-IR spectroscopy,and TGA experiments,respectively.The usage of H_(3)PMo_(12)O_(40) as source for Ni_(8)PMo_(8) resulted a sandwich like structure built from two Ni_(4)-thiacalix[4]arene units and a Mo_(8) polyoxometalate with inner spaces of PO_(4)^(3-).Ni_(8)Mo_(8) with the similar structure to that of Ni_(8)PMo_(8) is from H_(2)MoO_(4) starting reagent with OH^(-)and CO_(3)^(2-)anions encapsulated in the center.The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation.This work provides a better understanding of the structure-property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalatebased functional materials.

Sodium-based dual-ion batteries via coupling high-capacity selenium/graphene anode with high-voltage graphite cathode

Dual ion batteries(DIBs) exhibit broad application prospects in the field of electrical energy storage(EES)devices with excellent properties,such as high voltage,high energy density,and low cost.In the graphitebased DIBs,high voltage is needed to store enough anions with the formation of anion intercalation compound XCn(X=AlCl4-,PF6-,TFSI-,etc.).Hence,it is difficult for graphite-based DIBs to match proper anodes and electrolytes.Here,an Se/graphene composite is prepared via a convenient method,and assembled into a dual-ion full battery(DIFB) as anode with graphite cathode and 1 mol/L NaPF6 in EC:EMC(1:1,v:v).This DIFB has achieved a high discharge capacity of 75.9 mAh/g and high medium output voltage of 3.5 V at 0.1 A/g.Actually,the suitable anode materials,such as the present Se/graphene composite,are extremely important for the development and application of graphite-based DIBs.This study is enlightening for the design of future low-cost EES devices including graphite-based DIBs.

Copper-sulfide cluster assembled architecture via in situ reaction

A new copper-thiolate cluster assembled framework[Cu2(μ4-SCH3)Cl]n(1),has been solvothermally synthesized through in situ reaction viz.,in situ ligand generation and metal reduction.Compound 1 represents the first 3 D framework based on Atlas-sphere functionalized by singleμ2-Cl groups.DOS calculation reveals the interaction of electronic structures.It is found that the HOMO is mainly distributed on Cl,Cu and S bonding orbitals,while the LUMO is dominated by Cu-Cl antibonding orbitals.